Hydrogen production by biomass product depolarized water electrolysis

ABSTRACT

A process for hydrogen production by water electrolysis and a process of depolarizing the anode of a water electrolysis cell by oxidizing a biomass product which may be monosaccharides, lignins, and mixtures thereof. The process of this invention avoids molecular oxygen evolution and results in high purity hydrogen at cell potentials substantially less than required for normal water electrolysis involving oxygen evolution. The process utilizes biomass products which are readily available and cost effective. High consumption of biomass product is achieved with an anode of lead-rich ruthenium polychlore compounds.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of my application Ser. No.234,692, filed Feb. 17, 1981, now U.S. Pat. No. 4,341,608.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a process for production of hydrogen fromwater by electrolysis. More particularly, this invention relates todepolarizing the anode of a water electrolysis cell by oxidizing abiomass product which may be monosaccharides, lignins, and mixturesthereof, thereby avoiding molecular oxygen evolution. The process ofthis invention produces high purity hydrogen electrolytically at cellpotentials substantially less than required for normal waterelectrolysis involving oxygen evolution. The utilization of biomassproduct provides a cost effective material to depolarize the anode inwater electrolysis process. High consumption of biomass product has beenachieved with an anode of lead-rich ruthenium pyrochlore compounds.

2. Description of the Prior Art

The use of organic materials to reduce hydrogen overvoltage inelectrolysis of brine by addition of a hydroxy carboxylic acid and aphosphorus containing organic compound to the catholyte is taught byU.S. Pat. No. 3,954,581. The organic material added to the brine is notinvolved in any electrochemical reaction. U.S. Pat. No. 4,175,013teaches a method of production of oxygen and hydrogen from water inwhich formaldehyde is electrolyzed cathodically to hydrocarbons of lowmolecular weight such as methane and ethane, and water being anodicallyoxidized to oxygen. U.S. Pat. No. 4,160,816 teaches a high hydrogenovervoltage to increase production of formic acid and reduce hydrogenproduction at the cathode. U.S. Pat. No. 4,089,761 teaches a sewagetreatment process wherein oxygen for supply to aerobic or microorganismsis produced at the anode of an electrolytic cell meaintained in thebiodigestion compartment of the sewage treatment cell with the cathodebeing isolated so as to vent hydrogen out of the cell.

The electrolytic oxidation of dextrose in the manufacture of calciumgluconate is known as described in the article "Manufacture of CalciumGluconate by Electrolytic Oxidation of Dextrose" by H. S. Isbell,Harriet L. Frush and F. J. Bates, Industrial and Engineering Chemistry,Vol. XXIV, No. 4, April 1932, pps. 375-378, wherein it is taught thatCaBr₂ is necessary as a catalyst. The article "Electrolytic Preparationof Calcium Gluconate and Other Salts of Aldonic Acids" by Colin G. Finkand Donald B. Summers, Transactions of the Electrochemical Society, 74,625 (1938), teaches that alkali ferricyanide may be used as a substitutefor the alkali bromide as a catalyst in the electrolytic preparation ofcalcium gluconate. The commercial processes for oxidation of sugars toacids are indirect oxidations, that is, the electrochemical reaction isreduction of bromine followed by a subsequent chemical oxidationreaction.

The Applicant is not aware of prior art wherein a direct electrochemicaloxidation reaction oxidizing organic material in the electrolyte is usedfor depolarization of the anode of a water electrolysis cell therebyavoiding molecular oxygen evolution and reducing the electrolysis powerrequirements for the production of hydrogen. Nor is the applicant awareof any teachings of the high consumption of biomass product with use oflead-rich ruthenium pyrochlore compounds for the anode of such waterelectrolysis cells.

SUMMARY OF THE INVENTION

This invention relates to a process for hydrogen production by waterelectrolysis and a process of depolarizing the anode of a waterelectrolysis cell. An electrical potential is maintained across an anodein an anode zone and a cathode in a cathode zone of an electrolyticcell. In the anode zone, oxidizable biomass product selected from thegroup consisting of monosaccharides, lignins and mixtures thereof, isoxidized with aqueous electrolyte material producing an oxidized biomassproduct, hydrogen ions and electrons. The hydrogen ions are transportedthrough the electrolyte to the cathode zone, there forming molecularhydrogen.

The anode zone reaction may be written as Reaction I and the cathodezone reaction may be written as Reaction II, as follows:

Reaction I

    BP+xH.sub.2 O→(BP)O.sub.x +2xH.sup.+ +2xe.sup.-

wherein BP represents oxidizable biomass product selected from the groupconsisting of monosaccharides, lignins and mixtures thereof.

Reaction II

    2H.sup.+ +2e.sup.- →H.sub.2

The above reaction system operates at electrolysis voltage and powerrequirements for the electrolytic production of hydrogen by changing theelectrochemical reaction and avoiding the formation of molecular oxygen.The electrolysis cells of this invention operate at electricalpotentials of less than about 1.5 volts.

Lead-rich ruthenium pyrochlore compounds have been found to beparticularly suitable for use as anodes in the process of this inventionfor high consumption of biomass product and high CO₂ production.

Accordingly, it is an object of this invention to provide a process forhydrogen production by water electrolysis at cell potentials of lessthan 1.5 volts.

Another object of this invention is to provide a process for high purityhydrogen production by water electrolysis which avoids molecular oxygenevolution.

Yet another object of this invention is to provide a process forhydrogen production by water electrolysis involving directelectrochemical oxidation of cost effective oxidizable organic material.

Still another object of this invention is to provide a process fordepolarizing the anode of a water electrolysis cell by directelectrochemical oxidation of oxidizable biomass product.

These and other objects, advantages and features of this invention willbe apparent from the description taken together with the drawingdescribing preferred embodiments in detail.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically shows an electrolytic cell for use in the processfor hydrogen production by one embodiment of this invention;

FIG. 2 shows current-potential curves for a lead-rich rutheniumpyrochlore anode in basic electrolyte; and

FIG. 3 shows current-potential curves for a lead-rich rutheniumpyrochlore anode in acid electrolyte.

DESCRIPTION OF PREFERRED EMBODIMENTS

Referring to FIG. 1, the process for hydrogen production by biomassproduct depolarized water electrolysis may be conducted in electrolyticcell 5 comprising anode zone 7 with anode 13 and cathode zone 9 withcathode 11, the anode and cathode zones being separated by ion porousseparator 12. Separator 12 affords ionic interaction between the anodecompartment and the cathode compartment for ease of separate gasrecovery from the cell, but is not necessary for cell operation. Anelectrical potential is maintained across anode 13 and cathode 11 by anexternal bias circuit comprising power source 16 and variable control 17connected across anode electrical lead 14 and cathode electrical lead15. One of the features of this invention is that an electricalpotential of less than about 1.5 volts and preferably about 0.5 to about1.0 volts is suitable for the hydrogen production by biomass productdepolarized water electrolysis. Aqueous acid and basic electrolytes aresuitable for facilitating the hydrogen ion transfer from the anode zoneto the cathode zone. Oxidizable biomass product selected from the groupconsisting of monosaccharides, lignins and mixtures thereof are added toanode zone 7 by biomass product feed 18. By the electrochemical processtaking place in the anode zone, as set forth in Reaction I above, theoxidizable biomass product is oxidized with water to produce hydrogenions, electrons and oxidized biomass product. Complete oxidation of theoxidizable biomass product yields CO₂ which is withdrawn through anodezone gas withdrawal conduit 19, but generally, the oxidizable biomassproduct will not be fully oxidized, but oxidized to a degree ofoxidation less than CO₂. The electrolyte and liquid and solid oxidizedbiomass product may be withdrawn through anode zone withdrawal conduit30. Electrolyte treatment and recycle means 31 is provided to regenerateelectrolyte for recycle to the anode zone and may include suitablepumping means and separation means for withdrawal of oxidized biomassproduct through oxidized biomass product discharge conduit 32. Freshelectrolyte is then recycled back to anode zone 7 through conduits 35and 36 with provision for electrolyte makeup through conduit 33 andwater addition through conduit 34. Since water is consumed in theelectrochemical reaction taking place in anode zone 7, it may bedesirable to add water separate from electrolyte.

As shown in the figure, hydrogen ion transport takes place through theaqueous electrolyte with the hydrogen ions passing through separator 12into cathode zone 9 for the electrochemical reaction set forth inReaction II above for molecular hydrogen production. Molecular hydrogenis the only gaseous chemical product produced in cathode zone 9 and thusmay be withdrawn as pure molecular hydrogen through cathode zone gaswithdrawal conduit 20. Electrolyte makeup for cathode zone 9 is providedby electrolyte makeup conduit 39.

The process for hydrogen production by biomass product depolarized waterelectrolysis according to this invention may be carried out in anelectrolytic cell of any configuration known to the art and may beconducted in any manner known to the art so long as oxidizable biomassproduct is oxidized in the anode zone, hydrogen ions formed therebytransported through an electrolyte to the cathode zone and molecularhydrogen is formed in the cathode zone due to an electrical potentialmaintained between the anode and cathode. Accordingly, cell container 10may be of any suitable material and shape known to the art and may beused in association with other like or different type cells in variousmanners and relationships known to the art.

One of the important features of this invention is the use of oxidizablebiomass product selected from the group consisting of monosaccharides,lignins and mixtures thereof for reaction in the anode chamber. Thisavoids molecular oxygen evolution and reduces the electrolysis voltageand thereby, the power requirements for electrolytic production ofhydrogen. Monosaccharides are well known to be derivable from naturalbiomass materials produced by growing plants such as cellulose andhemicellulose. Any oxidizable monosaccharide is suitable for use in thisinvention including the hexoses and pentoses such as glucose, fructose,arabinose and xylose. When monosaccharides are used as the oxidizablebiomass product, it is preferred to use aqueous acidic electrolytes. Anylignin having an oxidizable functional group is satisfactory for use inthis invention, such as alkali lignins obtained by acidification of analkaline extract of wood and those obtained from other treatments ofcellulosic fibers. When lignins are used, it is suitable to use eitheralkaline or acidic electrolytes. When mixtures of monosaccharides andlignins are used as an oxidizable biomass product according to thisinvention, it is preferred to use acidic electrolytes. Thus, it is seenthat the oxidizable biomass product used for this invention representsreadily available and economic biomass products which are readilyrenewable. For example, glucose, a preferred monosaccharide, may bereadily derived from biomasses such as municipal wastes, agriculturalwastes and forest product wastes, while lignins, such as alkalinelignins may be derived from kraft pulping effluents. The oxidizablebiomass product may be added to the electrolytic cell in a water orelectrolyte solution. Suitable concentration of oxidizable biomassproduct monosaccharides in the electrolyte of the anode zone is about0.1 to 2.0 Molar, preferably about 0.8 to about 1.2 Molar. Suitableconcentration of oxidizable biomass product lignins in the electrolyteof the anode zone is about 10 to about 300 grams/liter, preferably about100 to 150 grams/liter.

Suitable electrolytes for use in the process of this invention includeaqueous acidic electrolytes, preferably those wherein the acid isselected from the group consisting of hydrochloric, sulfuric, perchloricand phosphoric acids. Suitable acid concentration in the aqueouselectrolytes is about 0.1 to 10 Molar, preferably about 0.5 to 1.5Molar. Suitable aqueous basic electrolytes include those having a baseconcentration of about 0.1 to 6 Molar, preferably wherein the base isselected from the group consisting of sodium hydroxide and potassiumhydroxide, It is preferred that the concentration of base in theelectrolyte be about 0.5 to 1.0 Molar.

Any suitable hydrogen ion passing separator materials may be used toseparate the anode zone from the cathode zone, particularly for ease ofgas collection. Suitable separator materials are well known in the artand include Nafion (a sulfonated perfluoropolyethylene sold by DuPont),nitrocellulose, cellulose acetate, and other fluorocarbon ion exchangemembranes.

Many suitable metallic electrode materials known to the art may be usedin the process of this invention such as platinized platinum,platinum-tungsten, platinum-tantalum, well known Raney alloys, nickel,and lead-rich ruthenium pyrochlore compounds. For high biomassconsumption and CO₂ production, it is preferred that the anode belead-rich ruthenium pyrochlore compounds such as those having theformula

    Pb.sub.2 [Ru.sub.2-x Pb.sub.x ]O.sub.7-y

wherein x is greater than 0 and less than or equal to about 1.2 and y isgreater than or equal to 0 and less than or equal to about 1.0. Furtherdisclosure of compounds according to the above formula and theirproduction is disclosed in U.S. Pat. No. 4,124,539.

The electrolytic cell may be operated at ambient pressures andtemperatures and preferably at somewhat higher than ambient temperaturesto promote the electrochemical oxidation of the organic material.Temperatures of above about 20° C. are suitable, and preferredtemperatures are in the range of about 60° to 90° C., about 70° to 90°being most preferred. The lead-rich ruthenium polychlore anode providesoperation in the lower temperatures of these ranges.

One of the important features of this invention is the reduction ofpower requirements for production of hydrogen by water electrolysis.This is achieved by the anode zone oxidation of oxidizable biomassproduct with electrical potentials of less than about 1.5 volts.Conventional water electrolysis requires about 1.5 to 2.0 volts.According to the process of this invention, electrical potential ofabout 0.5 to about 1.0 volts is suitable to generate current densitiesof greater than about 50 mA/cm². On the basis of standard free energiesof formation, a theoretical potential for the overall cell reactionusing glucose can be calculated to be +0.013 V, a spontaneous reaction.Thus, considerable overpotential can be tolerated while still retaininga potential well below that required for conventional waterelectrolysis. Voltages as low as 0.6 volts have been used inexperimental cells in the production of hydrogen by water electrolysisaccording to this invention wherein the anode is depolarized by use ofglucose.

This invention also includes the process of depolarizing the anode of awater electrolysis cell by oxidizing in the anode zone oxidizablebiomass products selected from the group consisting of monosaccharides,lignins and mixtures thereof with water producing oxidized biomassproduct, hydrogen ions and electrons, thereby avoiding molecular oxygenevolution. This is readily seen by reference to Reaction I set forthabove, the conditions for which have been set forth with respect to theprocess for hydrogen production described above.

Another feature of this invention is the production of useful productsby the oxidation of oxidizable biomass products, such as, for example,the production of acids, such as gluconic acid from the oxidation ofglucose and other oxidized products. These products may be isolated andmarketed as useful products.

The following examples are set forth in detail to illustrate specificembodiments of this invention and are not intended to limit theinvention.

EXAMPLE I

Lead-rich ruthenium polychlore compound having an average formula

    Pb.sub.2 [Ru.sub.1.82 Pb.sub.0.18 ]0.sub.7-y

was prepared by mixing Pb(NO₃)₂ and RuO₂ in amounts having a Pb to Ruratio of about 4/1 moles. The mixture was reacted in air at 400° C. for1.75 hours and at 600° C. for an additional 22 hours, with 5regrindings. The reacted powder was washed at room temperature in 0.1 Nacetic acid for 1.5 hours and then 0.05 N acetic acid for 1.7 hours toremove excess lead oxide. An electrode was made by Teflon bonding of thelead-rich ruthenium polychlore powder to a platinum screen currentcollector. Steady-state current-potential points were measured for alead-rich ruthenium polychlore electrode of about 3 cm² in 6.1 M KOH at25° C. The potential was increased in 6 steps/min. at 10 mV/step. Thepotential of the lead-rich ruthenium polychlore electrode was comparedto a Hg/HgO electrode. FIG. 2, by the dashed curve, shows thecurrent-potential curve. The current-potential curve was then measuredwith 0.50 M glucose added to the electrolyte and is shown in FIG. 2 bythe solid line. In FIG. 2, it is shown that in the presence of glucoseappreciable oxidative currents are generated prior to the voltage atwhich oxygen evolution occurs without the presence of added glucose. Thegas evolved when glucose was present was identified as CO₂. The shift tomore negative potentials is, for example, 375 mV at 100 mA at ambienttemperature.

EXAMPLE II

A lead-rich ruthenium polychlore electrode having a geometrical area of3 CM² was prepared as described in Example I. Steady-statecurrent-potential measurements were obtained in a 0.50 M H₂ SO₄electrolyte at 61° C. in the same manner as described in Example Iexcept that the lead-rich ruthenium polychlore electrode potential wascompared with a Standard Calomel Electrode (SCE). The results are shownin FIG. 3 with the dashed curve showing the acid electrolyte alone andthe solid curve showing the acid electrolyte with 0.50 M added glucose.FIG. 3 shows the cell current reaches appreciable values by oxidation ofglucose at potentials more negative than oxygen evolution in the acidelectrolyte alone, about 300 mV at 50 mA. The gas evolved when glucosewas present was identified as CO₂.

While in the foregoing specification this invention has been describedin relation to certain preferred embodiments thereof, and many detailshave been set forth for purpose of illustration, it will be apparent tothose skilled in the art that the invention is susceptible to additionalembodiments and that certain of the details described herein can bevaried considerably without departing from the basic principles of theinvention.

I claim:
 1. A process for hydrogen production by biomass productdepolarized water electrolysis comprising: maintaining an electricalpotential across an anode comprising metal selected from the groupconsisting of nickel and lead-rich ruthenium polychlore compounds havinga formula Pb₂ [Ru_(2-x) Pb_(x) ]0_(7-y) wherein x is greater than 0 andless than or equal to about 1.2 and y is greater than or equal to 0 andless than or equal to about 1.0 in a metallic anode zone and a metalliccathode in a cathode zone of an electrolytic cell; oxidizing, in anaqueous electrolyte in said electrolytic cell anode zone, oxidizablebiomass product selected from the group consisting of monosaccharides,lignins and mixtures thereof with water producing oxidized biomassproduct, hydrogen ions and electrons; transporting said hydrogen ionsthrough said electrolyte to said cathode zone; forming molecularhydrogen in said cathode zone.
 2. The process of claim 1 wherein saidanode comprises nickel.
 3. The process of claim 1 wherein said anodecomprises Pb₂ [Ru_(2-x) Pb_(x) ]0_(7-y).
 4. The process of claim 3wherein said lead-rich ruthenium polychlore has an average formula Pb₂[Ru₁.82 Pb₀.18 ]0_(7-y).
 5. The process of claim 1 wherein saidelectrical potential is less than about 1.5 volts.
 6. The process ofclaim 5 wherein said electrical potential is about 0.5 to about 1.0volts.
 7. The process of claim 1 wherein said biomass product comprisesmonosaccharide.
 8. The process of claim 7 wherein said monosaccharidecomprises glucose.
 9. The process of claim 7 wherein said monosaccharidehas a concentration of about 0.1 to about 2.0 Molar in said aqueouselectrolyte.
 10. The process of claim 9 wherein said monosaccharideconcentration is about 0.8 to about 1.2 Molar.
 11. The process of claim1 wherein said electrolyte comprises an aqueous acid of about 0.1 toabout 10 Molar concentration.
 12. The process of claim 11 wherein saidacid is selected from the group consisting of hydrochloric, sulfuric,perchloric and phosphoric and said concentration is about 0.5 to about1.5 Molar.
 13. The process of claim 11 wherein said biomass productcomprises monosaccharide in a concentration of about 0.1 to about 2.0Molar in said aqueous acid electrolyte.
 14. The process of claim 1wherein said electrolytic cell is maintained at temperatures above about20° C.
 15. The process of claim 14 wherein said temperatures are about60° to about 90° C.
 16. The process of claim 1 wherein said electrolyticcell is maintained at temperatures about 70° to about 90° C.
 17. Theprocess of claim 1 wherein said biomass product comprises lignin. 18.The process of claim 17 wherein said lignin has a concentration of about10 to about 300 grams/liter in said aqueous electrolyte.
 19. The processof claim 18 wherein said lignin concentration is about 100 to about 150grams/liter.
 20. The process of claim 17 wherein said electrolytecomprises an aqueous base of about 0.1 to about 6 Molar concentration.21. The process of claim 20 wherein said base is selected from the groupconsisting of sodium hydroxide and potassium hydroxide and saidconcentration is about 0.5 to about 1.0 Molar.
 22. The process of claim20 wherein said biomass product comprises lignin in a concentration ofabout 10 to about 300 grams/liter in said aqueous basic electrolyte. 23.The process of claim 17 wherein said electrolyte comprises an aqueousacid of about 0.1 to about 10 Molar concentration.
 24. The process ofclaim 23 wherein said acid is selected from the group consisting ofhydrochloric, sulfuric, perchloric and phosphoric and said concentrationis about 0.5 to about 1.5 Molar.
 25. The process of claim 1 wherein saidhydrogen ions are transported through a hydrogen ion passing separatorseparating said anode zone from said cathode zone.
 26. The process ofclaim 1 wherein said metallic cathode is selected from the groupconsisting of platinized platinum, platinum-tungsten, platinum tantalum,Raney alloys, nickel and lead-rich ruthenium polychlore compounds havinga formula Pb₂ [Ru_(2-x) Pb_(x) ]O_(7-y).
 27. A process of depolarizingthe anode of a water electrolysis cell having an electrical potentialacross a metallic anode selected from the group consisting of nickel andlead-rich ruthenium polychlore compounds having a formula Pb₂ [Ru_(2-x)Pb_(x) ]O_(7-y) wherein x is greater than 0 and less than or equal toabout 1.2 and y is greater than or equal to 0 and less than or equal toabout 1.0 in an anode zone and a metallic cathode in a cathode zonecomprising: oxidizing in said anode zone oxidizable biomass productselected from the group consisting of monosaccharides, lignins andmixtures thereof with water producing oxidized biomass product, hydrogenions and electrons, thereby avoiding molecular oxygen evolution.
 28. Theprocess of claim 27 wherein said anode comprises nickel.
 29. The processof claim 27 wherein said anode comprises Pb₂ [Ru_(2-x) Pb_(x) ]O_(7-y).30. The process of claim 29 wherein said lead-rich ruthenium polychlorehas an average formula Pb₂ [Ru₁.82 Pb₀.18 ]O_(7-y).
 31. The process ofclaim 27 wherein said electrical potential is less than about 1.5 volts.32. The process of claim 27 wherein said electrical potential is about0.5 to about 1.0 volts.
 33. The process of claim 27 wherein said biomassproduct comprises monosaccharide.
 34. The process of claim 33 whereinsaid monosaccharide comprises glucose.
 35. The process of claim 33wherein said monosaccharide has a concentration of about 0.1 to about2.0 Molar in said aqueous electrolyte.
 36. The process of claim 35wherein said monosaccharide concentration is about 0.8 to about 1.2Molar.
 37. The process of claim 27 wherein said electrolyte comprises anaqueous acid of about 0.1 to about 10 Molar concentration.
 38. Theprocess of claim 37 wherein said acid is selected from the groupconsisting of hydrochloric, sulfuric, perchloric and phosphoric and saidconcentration is about 0.5 to about 1.5 Molar.
 39. The process of claim37 wherein said biomass product comprises monosaccharide in aconcentration of about 0.1 to about 2.0 Molar in said aqueous acidelectrolyte.
 40. The process of claim 27 wherein said electrolytic cellis maintained at temperatures above about 20° C.
 41. Thr process ofclaim 40 wherein said temperatures are about 60° to about 90° C.
 42. Theprocess of claim 27 wherein said electrolytic cell is maintained attemperatures about 70° to about 90° C.
 43. The process of claim 27wherein said biomass product comprises lignin.
 44. The process of claim43 wherein said lignin has a concentration of about 10 to about 300grams/liter in said aqueous electrolyte.
 45. The process of claim 44wherein said lignin has a concentration of about 100 to about 150grams/liter in said aqueous electrolyte.
 46. The process of claim 27wherein said electrolyte comprises an aqueous base of about 0.1 to about6 Molar concentration.
 47. The process of claim 46 wherein said base isselected from the group consisting of sodium hydroxide and potassiumhydroxide and said concentration is about 0.5 to about 1.0 Molar. 48.The process of claim 46 wherein said biomass product comprises lignin ina concentration of about 10 to about 300 grams/liter in said aqueousbasic electrolyte.
 49. The process of claim 27 wherein said electrolytecomprises an aqueous acid of about 0.1 to about 10 Molar concentration.50. The process of claim 49 wherein said acid is selected from the groupconsisting of hydrochloric, sulfuric, perchloric and phosphoric and saidconcentration is about 0.5 to about 1.5 Molar.
 51. The process of claim27 wherein said hydrogen ions are transported through a hydrogen ionpassing separator separating said anode zone from said cathode zone. 52.The process of claim 27 wherein said metallic cathode is selected fromthe group consisting of platinized platinum, platinum-tungsten, platinumtantalum, Raney alloys, nickel and lead-rich ruthenium polychlorecompounds having a formula Pb₂ [Ru_(2-x) Pb_(x) ]O_(7-y).